EP1990382B1 - Tintensatz, Tintenstrahlaufzeichnungsverfahren, Tintenpatrone, Aufzeichnungseinheit, Tintenstrahlaufzeichnungsverfahren und wässrige Tinte - Google Patents

Tintensatz, Tintenstrahlaufzeichnungsverfahren, Tintenpatrone, Aufzeichnungseinheit, Tintenstrahlaufzeichnungsverfahren und wässrige Tinte Download PDF

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Publication number
EP1990382B1
EP1990382B1 EP08155981.7A EP08155981A EP1990382B1 EP 1990382 B1 EP1990382 B1 EP 1990382B1 EP 08155981 A EP08155981 A EP 08155981A EP 1990382 B1 EP1990382 B1 EP 1990382B1
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EP
European Patent Office
Prior art keywords
ink
surface tension
dynamic surface
lifetime
milliseconds
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EP08155981.7A
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English (en)
French (fr)
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EP1990382A1 (de
Inventor
Kenji Moribe
Satoshi Kudo
Mikio Sanada
Hideki Yamakami
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Canon Inc
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Canon Inc
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Priority claimed from JP2008112758A external-priority patent/JP5932199B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/40—Ink-sets specially adapted for multi-colour inkjet printing

Definitions

  • the present invention relates to an aqueous ink, an ink set, an ink jet recording method, an ink cartridge, a recording unit, and an ink jet recording method.
  • the gradation can be improved by reducing the area of one dot formed from ink on the recording medium.
  • a plurality of dots are apt to link with each other, so it may be unable to strictly control the area of the surface of the recording medium coated with the ink even when the amount of the ink to be applied per unit area is increased or decreased.
  • a plurality of dots is apt to link with each other, so the blurring of the ink is apt to occur on the recording medium in some cases.
  • the blurring of ink is suppressed by setting the surface tension of the ink in a bubble period T (second/bubble) of 0.2 or less to be 40 mN/m or more, and the ejection reliability of the ink is improved by setting the surface tension of the ink in a bubble period T (second/bubble) of more than 1 to be less than 50 mN/m.
  • the ejection reliability of ink is improved by setting the dry viscosity of the ink to be 100 mPa ⁇ s or less, and the dynamic surface tension characteristic of the ink at a specific lifetime is specified.
  • the blurring of the ink is suppressed by setting the dynamic surface tension of the ink at a lifetime of 10 milliseconds to 45 mN/m or more, and the quick-drying property of the ink is improved by setting the dynamic surface tension of the ink at a lifetime of 1,000 milliseconds to be 35 mN/m or less.
  • the dynamic surface tensions of the respective inks at a temperature of 25°C and the same lifetime in the lifetime range of 30 milliseconds to 1,000 milliseconds by a maximum bubble pressure method are specified as follows: (1) the dynamic surface tension of the yellow ink is equal to or larger than that of the black ink, (2) a difference in dynamic surface tension between the yellow ink and the black ink is 5 mN/m or less, (3) a difference in dynamic surface tension between the yellow ink and the magenta ink, and a difference in dynamic surface tension between the yellow ink and the cyan ink are each 3 mN/m or more, and (4) the dynamic surface tension of each of the magenta ink and the cyan ink is lower than that of the black ink.
  • those specifications prevent different colors from mixing with each other at a boundary portion between them on plain paper.
  • WO 2007/120703 A2 a document according to Art 54(3) EPC, pertains to an aqueous based magenta inkjet ink comprising a certain specified combination of soluble magenta colorants.
  • EP-A-1 186 413 describes a recording unit comprising an ink housing part for housing an ink containing a coloring material and an aqueous medium.
  • EP-A-1 085 062 describes a method of recording a multi-color image containing a plurality of image regions formed by applying an black ink and a color ink to overlap each other in different orders.
  • US 2005/263035 A1 describes an ink set, an inkjet recording apparatus including the ink set, which include a black ink composition comprising a first colorant, water, and a first alkyl ether and a color ink composition comprising a second colorant, water, and a second alkyl ether.
  • US-B1-6 641 257 describes an ink for thermal ink jet printing which contains at least an aqueous vehicle, a dye and a light stabilizer.
  • US 2003/130374 A1 describes a set of inks comprising (1) a first ink having a first color and comprising water, a first colorant, and at least one of (a) a cationic polymer, (b) a cationic surfactant, or (c) an inorganic salt the cation of which has a tetraphenylboride salt that is substantially insoluble in water, and (2) a second ink having a second color different from the first color and comprising water, a second colorant, and sodium tetraphenylboride.
  • EP-A-1 182 237 describes an ink set including red (or magenta) ink(s), blue (or cyan) ink(s), yellow ink(s) and optionally a black ink, where each ink contains water-soluble dye(s), water as solvent, drying retardant(s) and optionally preservatives and/or other additives.
  • EP-A-1 004 641 describes an ink composition which comprises an alkali-soluble colorant, a water-soluble organic solvent, water, and a cationic water-soluble resin.
  • 2006-63322 can improve the gradation of an image while maintaining color uniformity in the image when plain paper or the like is used as a recording medium.
  • an ink capable of forming such ideal dots as described below has not been present in which, when plain paper or the like is used as a recording medium, the spread of the ink in a lateral direction (gradation) and color uniformity (the uniform wetting of the surface of the recording medium with the ink) are appropriately controlled.
  • the inventors of the present invention have made investigation into an ink capable of solving the above problems by concentrating attention on the behavior of the ink during a period commencing on the application of the ink to a recording medium and ending on the completion of the permeation of the ink into the recording medium with the dynamic surface tension of the ink appropriately controlled when plain paper or the like is used as the recording medium.
  • the first object of the present invention is to provide an ink set including inks with their dynamic surface tensions controlled, the ink set being capable of suppressing bleeding in, for example, a recording medium having an ink-receiving layer.
  • the second object of the present invention is to provide an ink set including aqueous inks capable of improving gradation while maintaining color uniformity when plain paper or the like is used as a recording medium, the ink set being capable of suppressing bleeding in, for example, a recording medium having an ink-receiving layer.
  • another object of the present invention is to provide an ink jet recording method, an ink cartridge, a recording unit, and an ink jet recording method each using the aqueous inks of which the ink set is composed.
  • another object of the present invention is to provide aqueous inks for use in an ink set capable of suppressing bleeding in, for example, a recording medium having an ink-receiving layer.
  • an ink set according to the first embodiment of the present invention is an ink set including a plurality of aqueous inks each containing a dye as a coloring material, in which: the ink set has at least a first aqueous ink containing a dye; the difference between dynamic surface tension of the first aqueous ink at a lifetime of 50 milliseconds and dynamic surface tension of the first aqueous ink at a lifetime of 500 milliseconds is 7 mN/m or more; and, between the first aqueous ink and at least one type of aqueous ink except the first aqueous ink included in the ink set, dynamic surface tension ⁇ a (mN/m) of an ink A having relatively higher lightness at a lifetime of 500 milliseconds and dynamic surface tension ⁇ b (mN/m) of an ink B having relatively lower lightness at a lifetime of 500 milliseconds satisfy a relationship of -5
  • an ink set according to the second embodiment of the present invention includes a plurality of aqueous inks each containing a dye as a coloring material, in which: the ink set has at least a first aqueous ink containing a dye; the first aqueous ink satisfies the following conditions (1) to (3): (1) dynamic surface tension at a lifetime of 50 milliseconds is from 42 mN/m or more to less than 49 mN/m, (2) dynamic surface tension at a lifetime of 500 milliseconds is from 28 mN/m or more to 38 mN/m or less, and (3) the difference between dynamic surface tension at a lifetime of 50 milliseconds and dynamic surface tension at a lifetime of 500 milliseconds is 7 mN/m or more; and, between the first aqueous ink and at least one type of aqueous ink except the first aqueous ink included in the ink set, dynamic surface tension ⁇ a (mN/m) of an ink A having
  • an ink set according to the third embodiment of the present invention includes at least three types of aqueous inks each containing a dye as a coloring material, in which: the ink set has at least a first aqueous ink containing a dye as a coloring material; the first aqueous ink satisfies the following conditions (1) to (3): (1) dynamic surface tension at a lifetime of 50 milliseconds is from 42 mN/m or more to less than 49 mN/m, (2) dynamic surface tension at a lifetime of 500 milliseconds is from 28 mN/m or more to 38 mN/m or less, and (3) the difference between dynamic surface tension at a lifetime of 50 milliseconds and dynamic surface tension at a lifetime of 500 milliseconds is 7 mN/m or more; and, among any two types of aqueous inks arbitrarily selected from the at least three types of aqueous inks included in the ink set, dynamic surface tension ⁇ a (mN/m) of an
  • an ink jet recording method includes ejecting ink by an ink jet method, in which the ink includes the aqueous inks of which the ink set is composed.
  • an ink cartridge includes an ink storing portion for storing ink, in which the ink contained in the ink storing portion is any one of the aqueous inks of which the ink set is composed.
  • a recording unit includes an ink storing portion for storing ink and a recording head for ejecting the ink, in which the ink contained in the ink storing portion includes the aqueous inks of which the ink set is composed.
  • an ink jet recording apparatus includes an ink storing portion for storing ink and a recording head for ejecting the ink, in which the ink contained in the ink storing portion includes the aqueous inks of which the ink set is composed.
  • an ink according to still another embodiment of the present invention is a first aqueous ink which includes a dye and is used for an ink set having a plurality of aqueous inks each containing a dye, in which the difference between dynamic surface tension at a lifetime of 50 milliseconds of the first aqueous ink and dynamic surface tension at a lifetime of 500 milliseconds of the first aqueous ink is 7 mN/m or more; and, between the first aqueous ink and at least one type of aqueous ink except the first aqueous ink included in the ink set, dynamic surface tension ⁇ a (mN/m) of an ink A having a relatively higher lightness at a lifetime of 500 milliseconds and dynamic surface tension ⁇ b (mN/m) of an ink B having a relatively lower lightness at a lifetime of 500 milliseconds satisfy a relationship of -5 ⁇ ( ⁇ a - ⁇ b ) 3.
  • an ink set can be provided including inks with their dynamic surface tensions controlled, the ink set being capable of suppressing bleeding in, for example, a recording medium having an ink-receiving layer.
  • an ink set can be provided including aqueous inks capable of improving gradation while maintaining color uniformity when plain paper or the like is used as a recording medium, the ink set being capable of suppressing bleeding in, for example, a recording medium having an ink-receiving layer.
  • the present invention can provide an ink cartridge, a recording unit, and an ink jet recording method each using the aqueous inks of which the ink set is composed.
  • the present invention can provide aqueous inks for use in an ink set capable of suppressing bleeding in, for example, a recording medium having an ink-receiving layer.
  • an aqueous ink is referred to also as “ink”
  • a first aqueous ink is referred to also as “first ink”.
  • the term "bleeding" as used in the present invention refers to unintended bleeding occurring at a boundary portion between images formed by using a plurality of inks each containing a dye in an aqueous ink set when these images are adjacent to each other.
  • the maximum bubble pressure method used in the measurement of the dynamic surface tension in the present invention is a method described below.
  • the maximum bubble pressure method is a method that a maximum pressure required to release a bubble formed at a tip portion of a probe (capillary) dipped in a liquid to be measured is measured, and a surface tension is found from this maximum pressure.
  • the lifetime (surface age) means a time from a point of time a surface of a new bubble is formed after a bubble has been released from the tip portion to a point of time of a maximum bubble pressure (a point of time the curvature radius of the bubble becomes equal to the radius of the tip portion of the probe) upon the formation of the bubble at the tip portion of the probe in the maximum bubble pressure method.
  • the dynamic surface tension in the present invention is a value measured at 25°C.
  • the first object of the present invention i.e., the suppression of bleeding occurring remarkably when an image is formed on, for example, a recording medium having an ink-receiving layer by using an ink set including inks with their dynamic surface tensions controlled
  • the inventors of the present invention have conducted investigation into the above bleeding by using various inks prepared so as to differ from each other in characteristic in which dynamic surface tension changes. As a result, the inventors have found that bleeding occurs remarkably when an image is formed on, for example, a recording medium having an ink-receiving layer by using an ink set including inks with some dynamic surface tension characteristics.
  • the inventors have found that bleeding occurs in an unexpectedly conspicuous state in an ink set including an ink the dynamic surface tension of which changes to such a large extent that the difference between the dynamic surface tension of the ink at a lifetime of 50 milliseconds and the dynamic surface tension of the ink at a lifetime of 500 milliseconds is 7 mN/m or more.
  • a recording medium having an ink-receiving layer has an extremely small void, and the void is present as a pore, so the permeation of ink into the recording medium having an ink-receiving layer occurs via a capillary action. Accordingly, the phenomenon occurring in this case is largely different from that occurring in the case where plain paper or the like is used as a recording medium.
  • the inventors of the present invention have conducted investigation into the behavior of ink when, for example, a recording medium having an ink-receiving layer is used during a period commencing on the application of the ink to the recording medium and ending on the permeation of the ink into the recording medium.
  • the permeation of the ink into the recording medium having an ink-receiving layer occurs via a capillary action.
  • capillary force is proportional to the surface tension of the liquid.
  • a site where the gas-liquid interface of the ink and the wall surface of the void in the recording medium are brought into contact with each other in other words, a site where capillary force is exerted is renewed at all times during movement of the ink. Accordingly, a surface tension that exerts the capillary force may correspond to not the static surface tension of the ink but the dynamic surface tension of the ink at a certain lifetime.
  • the inventors of the present invention have conducted investigation into the lifetime of dynamic surface tension that affects capillary force during movement of an ink in a void in a recording medium having an ink-receiving layer by using various ink sets including inks different from each other in characteristic in which a dynamic surface tension changes.
  • the inventors have found that the dynamic surface tension of the ink at a lifetime of 500 milliseconds rather than the static surface tension of the ink is dominant in an influence on the behavior of the ink at that time.
  • an ink having lower dynamic surface tension at a lifetime of 500 milliseconds flows into an ink having higher dynamic surface tension at a lifetime of 500 milliseconds, with the result that bleeding occurs.
  • an ideal approach to suppressing bleeding is to set the dynamic surface tensions of two types of inks at a lifetime of 500 milliseconds to be equal to each other.
  • a difference in dynamic surface tension at a lifetime of 500 milliseconds between the two types of the inks is extremely small, no such bleeding as to be substantially observed with the eyes is considered to occur.
  • the inventors of the present invention have conducted investigation into a relationship between the threshold value of a difference in dynamic surface tension at a lifetime of 500 milliseconds and the extent of bleeding by using various ink sets. As a result, the inventors have found that setting a difference in dynamic surface tension at a lifetime of 500 milliseconds between two types of inks to 3 mN/m or less suffices for the suppression of such bleeding as to be substantially observed with the eyes.
  • ⁇ a and ⁇ b more preferably satisfy the condition of -3 ⁇ ( ⁇ a - ⁇ b ) ⁇ 3, or particularly preferably satisfy the condition of -3 ⁇ ( ⁇ a - ⁇ b ) ⁇ 3.
  • the threshold value of the difference in dynamic surface tension at a lifetime of 500 milliseconds between two types of inks with which bleeding can be suppressed varies depending on a relative lightness relationship between the two types of the inks. This is due to the following reasons. Bleeding occurring when an ink having a relatively high lightness flows into an ink having relatively lower lightness is difficult to observe with the eyes, so some degree of increase in difference in dynamic surface tension at a lifetime of 500 milliseconds between the inks is accepted.
  • the lightness of each of the inks of which the ink set is composed must be measured while the same recording medium and the same recording duty are adopted for the inks.
  • Any recording medium can be used as the recording medium as long as the recording medium is applicable to an ordinary ink jet recording apparatus, and has an ink-receiving layer. Then, solid images in which the amounts of the respective inks of which the ink set is composed to be applied are uniformized are formed on the recording medium by using the inks, and the image portion is subjected to color measurement with, for example, a spectrophotometer, whereby a value for the lightness of each of the inks can be obtained.
  • the inks are preferably applied in amounts enough to coat the entirety of the surface of the recording medium.
  • a PR-101 manufactured by Canon Inc.
  • the color measurement can be performed with, for example, a spectrophotometer (trade name: Spectrolino; manufactured by Gretag Macbeth).
  • the amount of each ink to be applied is preferably, for example, about 10 ng per one pixel at a resolution of 600 ppi.
  • the present invention is, of course, not limited to such a recording medium, a spectrophotometer, and amounts of inks to be applied as described above.
  • the inventors of the present invention have conducted investigation into conditions specified for suppressing bleeding in the present invention. To be specific, the inventors have confirmed the following for a relative lightness relationship specified between two types of inks, the ink A and the ink B, of the a plurality of inks of which the ink set is composed, and a relative relationship specified between the dynamic surface tensions of the two types of the inks at a lifetime of 500 milliseconds.
  • bleeding performance does not depend on: the amount of each of the ink A and the ink B to be applied per unit area; the order in which the ink A and the ink B are applied to a recording medium; or the number of recording paths of each of the inks.
  • the two types of the inks are largely different from each other in amount to be applied, for example, when the amount of the ink B having relatively lower lightness to be applied is smaller than the amount of the ink A having relatively higher lightness to be applied, a lightness relationship between the images formed from the ink A and the ink B may be reversed as compared with that in the case where the two types of the inks are not largely different from each other in amount to be applied.
  • the lightness relationship between the respective images formed under the above predetermined conditions is reversed depending on whether the amount of each ink to be applied is large or small despite the fact that inks corresponding to the ink A and the ink B are determined from the lightness relationship, no such bleeding as to be observed with the eyes occurs.
  • a relationship between the dynamic surface tensions of a plurality of inks at a lifetime of 500 milliseconds and a lightness relationship between the inks are dominant in the occurrence of bleeding, so there is no need to take a hue or chroma relationship between the a plurality of inks into consideration.
  • a relationship between the dynamic surface tensions of a plurality of inks at a lifetime of 500 milliseconds and a lightness relationship between the inks specified by the present invention for suppressing bleeding are similarly applicable to various inks.
  • the specifications of the present invention are applicable to each of, for example, black, red, green, blue, light cyan, light magenta, and gray inks as well as each of cyan, magenta, and yellow inks used in an ordinary ink jet recording system. Further, the specifications of the present invention are applicable also to, for example, a clear ink used for improving, for example, the gloss and fastness of an image. Examples concerning those respective inks are not listed here, but are included in the present invention. In the present invention, it is more preferable that the ink A and the ink B described above are a magenta ink and a cyan ink, respectively. The present invention is, of course, not limited to the foregoing.
  • An ink set according to the first embodiment of the present invention has the following constitution. That is, the ink set, which has a plurality of inks each containing a dye, has at least an ink in which the difference between the dynamic surface tension of the ink at a lifetime of 50 milliseconds and the dynamic surface tension of the ink at a lifetime of 500 milliseconds is 7 mN/m or more (hereinafter referred to as "first ink").
  • an ink having relatively higher lightness between the first ink and at least one type of ink except the first aqueous ink included in the ink set is defined as an ink A
  • an ink having relatively lower lightness between the first ink and the at least one type of ink is defined as an ink B.
  • the dynamic surface tension ⁇ a (mN/m) of the ink A at a lifetime of 500 milliseconds and the dynamic surface tension ⁇ b (mN/m) of the ink B at a lifetime of 500 milliseconds must satisfy the relationship of -5 ⁇ ( ⁇ a - ⁇ b ) ⁇ 3.
  • the inventors of the present invention have conducted further investigation into the first object of the present invention. As a result, the inventors have reached the conclusion that, based on the lightness of the ink, it is possible to technically settle the bleeding problem occurring when the first ink is used in which the difference between the dynamic surface tension of the ink at a lifetime of 50 milliseconds and the dynamic surface tension of the ink at a lifetime of 500 milliseconds is 7 mN/m or more.
  • an ink according to another embodiment of the present invention has the following constitution. That is, the ink is a first ink which contains a dye and is used for an ink set having a plurality of inks each containing a dye, in which the difference between the dynamic surface tension of the ink at a lifetime of 50 milliseconds and the dynamic surface tension of the ink at a lifetime of 500 milliseconds is 7 mN/m or more.
  • an ink having relatively higher lightness between the first ink and at least one type of ink except the first aqueous ink included in the ink set is defined as an ink A
  • an ink having relatively lower lightness between the first ink and the at least one type of ink is defined as an ink B.
  • the dynamic surface tension ⁇ a (mN/m) of the ink A at a lifetime of 500 milliseconds and the dynamic surface tension ⁇ b (mN/m) of the ink B at a lifetime of 500 milliseconds must satisfy the relationship of -5 ⁇ ( ⁇ a - ⁇ b ) ⁇ 3.
  • the second object of the present invention that is, the suppression of the above bleeding and an improvement in gradation while color uniformity is maintained when plain paper or the like is used as a recording medium, will be described below.
  • One technical idea for achieving the above second object is as follows: in order that the gradation of an image can be improved by controlling the area of one dot to be proper, the spread of ink immediately after application of the ink to a recording medium is suppressed, and, furthermore, the ink is caused to permeate quickly into the recording medium while the spread of the ink is suppressed.
  • another technical idea for achieving the above second object is to impart to the ink wettability sufficient for voids present between fibers from which the recording medium is formed in order that color uniformity in the image can be improved.
  • the inventors of the present invention have conducted the following investigation into a state that ink spreads on a recording medium.
  • the inventors have prepared various inks different from each other in characteristic in which dynamic surface tension changes with a lifetime, and have recorded a one-dot ruled line on each of various recording media such as plain paper by using each of those inks.
  • the inventors have investigated a relationship between the line width of the ruled line and each of the dynamic surface tension and static surface tension of each of the inks from a lifetime of 10 milliseconds to a lifetime of 5,000 milliseconds.
  • the inventors have found that the line width of the ruled line and the dynamic surface tension of each of the inks at a lifetime of 50 milliseconds show the strongest correlation with each other in each of all types of investigated recording media.
  • the correlation continuously weakens as a lifetime deviates forward or backward from a lifetime of 50 milliseconds as a center.
  • the inventors of the present invention have gained the knowledge that investigation into the dynamic surface tension of each of the inks at a lifetime of 50 milliseconds enables the line width of the ruled line, that is, a state that the ink spreads on each of the recording media, to be specified.
  • the line width of the ruled line is measured after a recorded matter has been left standing overnight.
  • the inventors of the present invention have conducted further investigation while concentrating attention on the dynamic surface tension characteristic of each of the inks at a lifetime of 50 milliseconds.
  • the inventors have prepared inks with their dynamic surface tensions at a lifetime of 50 milliseconds variously changed, have formed an image by using each of these inks, and have investigated a relationship between gradation in the resultant image and the dynamic surface tension of each of the inks at a lifetime of 50 milliseconds.
  • the inventors have gained the knowledge that when setting the dynamic surface tension of each of the inks at a lifetime of 50 milliseconds to be 42 mN/m or more, the excessive spread of each of the inks on a recording medium can be suppressed.
  • the inventors of the present invention consider the reason why there is a high correlation between a state where ink spreads on a recording medium and the dynamic surface tension of the ink at a lifetime of 50 milliseconds to be as described below. That is, at a time point of 50 milliseconds from the application of the ink to the recording medium, at least part of the ink permeates into a region near the surface of the recording medium, and the region is one important factor for determining the area of one dot formed from the ink on the recording medium.
  • a change in the contact angle between the ink and the recording medium due to a change in the value of the dynamic surface tension of the ink after application of the ink to the recording medium is considered also to be a factor for determining the area of one dot formed of the ink on the recording medium.
  • evaporation of, for example, moisture in the ink immediately after being applied onto the recording medium occurs relatively more frequently as compared with the ink permeating in the thickness direction of the recording medium.
  • the amount in which the ink permeates in the thickness direction of the recording medium is considered to depend also on the dynamic surface tension of the ink at a lifetime of 50 milliseconds, and the dependence is considered also to be another important factor for determining the area of one dot formed of the ink on the recording medium.
  • the area of one dot formed from the ink on the recording medium can be made appropriate.
  • Investigation conducted by the inventors of the present invention has shown that, to be specific, a reduction in dynamic surface tension of the ink by 7 or more in the lifetime range of 50 milliseconds to 500 milliseconds suffices for the occurrence of such a phenomenon.
  • an ink having the following characteristics provides excellent image gradation: the ink has a dynamic surface tension of 42 mN/m or more at a lifetime of 50 milliseconds, and the difference between the dynamic surface tension of the ink at a lifetime of 50 milliseconds and the dynamic surface tension of the ink at a lifetime of 500 milliseconds is 7 mN/m or more. Further, the gradation can be particularly improved when the difference between the dynamic surface tension of the ink at a lifetime of 50 milliseconds and the dynamic surface tension of the ink at a lifetime of 500 milliseconds is 10 mN/m or more.
  • a dye in ink need be uniformly fixed to the recording medium.
  • a state that the ink is uniformly fixed refers to not a state that the dye in the ink is taken in a relatively large void present in the plain paper or the like as a recording medium so as to localize but a state that fibers of which the recording medium is composed is uniformly dyed with the dye in the ink.
  • the ink is required to exert wettability for pores such as voids between fibers.
  • the inventors of the present invention have conducted investigation into physical properties needed for causing the ink to have wettability for the pore. As a result, the inventors have found that the dynamic surface tension of the ink at a lifetime of 500 milliseconds must be appropriately determined. To be specific, the inventors have found that the dynamic surface tension of the ink at a lifetime of 500 milliseconds must be 38 mN/m or less. That is, the inventors of the present invention have gained the knowledge that in order to simultaneously improve both of an improvement in color uniformity and an improvement in gradation, the ink is required to have the following dynamic surface tension characteristics.
  • an ink having the following characteristics is preferable: the dynamic surface tension of the ink at a lifetime of 50 milliseconds is 42 mN/m or more, the difference between the dynamic surface tension of the ink at a lifetime of 50 milliseconds and the dynamic surface tension of the ink at a lifetime of 500 milliseconds is 7 mN/m or more, and the dynamic surface tension of the ink at a lifetime of 500 milliseconds is 38 mN/m or less.
  • the dynamic surface tension of the ink at a lifetime of 50 milliseconds is 49 mN/m or more, even when the extent to which the dynamic surface tension of the ink is reduced after the lifetime is large, higher priority is placed on the spread of the ink on the surface of the recording medium than on the permeation of the ink in the thickness direction of the recording medium. As a result, the area of one dot increases, and gradation cannot be obtained in some cases. Accordingly, the dynamic surface tension of the ink at a lifetime of 50 milliseconds is preferably from 42 mN/m or more to less than 49 mN/m.
  • the dynamic surface tension of the ink at a lifetime of 500 milliseconds is excessively low, specifically, less than 28 mN/m, higher priority is placed on the permeation of the ink into the recording medium than on the wetting of the voids between the fibers with the ink.
  • the ink easily permeates into the recording medium (in the thickness direction of the recording medium), so a phenomenon in which the ink comes out of the back surface of the recording medium, that is, strike-through may occur.
  • the dynamic surface tension of the ink at a lifetime of 500 milliseconds is preferably from 28 mN/m or more to 38 mN/m or less.
  • the dynamic surface tension of the ink at a lifetime of 500 milliseconds is particularly preferably from 32 mN/m or more to 38 mN/m or less.
  • the difference between the dynamic surface tension of the ink at a lifetime of 50 milliseconds and the dynamic surface tension of the ink at a lifetime of 500 milliseconds is preferably large from the viewpoint of the promotion of the permeation of the ink into the recording medium after a region where the ink permeates into the recording medium at a lifetime of 50 milliseconds has been determined to some extent.
  • the dynamic surface tension of the ink at a lifetime of 500 milliseconds must be 28 mN/m or more.
  • the difference between the dynamic surface tension of the ink at a lifetime of 50 milliseconds and the dynamic surface tension of the ink at a lifetime of 500 milliseconds is preferably equal to or lower than (the value of the dynamic surface tension of the ink at a lifetime of 50 milliseconds (mN/m) - 28 (mN/m)). Further, the difference between the dynamic surface tension of the ink at a lifetime of 50 milliseconds and the dynamic surface tension of the ink at a lifetime of 500 milliseconds is more preferably less than 21 mN/m.
  • first ink an ink capable of improving gradation while maintaining color uniformity when plain paper or the like is used as a recording medium
  • first ink must satisfy the following conditions (1) to (3): (1) the first ink has a dynamic surface tension of from 42 mN/m or more to less than 49 mN/m at a lifetime of 50 milliseconds, (2) the first ink has a dynamic surface tension of from 28 mN/m or more to 38 mN/m or less at a lifetime of 500 milliseconds, and (3) the difference between the dynamic surface tension of the first ink at a lifetime of 50 milliseconds and the dynamic surface tension of the first ink at a lifetime of 500 milliseconds is 7 mN/m or more.
  • An ink set according to the second embodiment of the present invention has the following constitution. That is, the ink set, which has a plurality of inks each containing a dye, has at least a first ink satisfying the conditions (1) to (3) described above. In addition, between the first ink and at least one type of ink except the first aqueous ink included in the ink set, an ink having relatively higher lightness is defined as an ink A, and an ink having relatively lower lightness is defined as an ink B.
  • the dynamic surface tension ⁇ a (mN/m) of the ink A at a lifetime of 500 milliseconds and the dynamic surface tension ⁇ b (mN/m) of the ink B at a lifetime of 500 milliseconds must satisfy the relationship of -5 ⁇ ( ⁇ a - ⁇ b ) ⁇ 3.
  • an ink set according to the third embodiment of the present invention has the following constitution. That is, the ink set, which has at least three types of inks each containing a dye, has at least a first ink satisfying the conditions (1) to (3) described above. In addition, among two types of inks arbitrarily selected from the at least three types of inks included in the ink set, an ink having relatively higher lightness is defined as an ink A, and an ink having relatively lower lightness is defined as an ink B.
  • the dynamic surface tension of the ink A at a lifetime of 500 milliseconds is represented by ⁇ a (mN/m)
  • the dynamic surface tension of the ink B at a lifetime of 500 milliseconds is represented by ⁇ b (mN/m).
  • the relationship of -5 ⁇ ( ⁇ a - ⁇ b ) ⁇ 3 must be valid.
  • part of the combinations of two types of inks may be free of the first ink.
  • the occurrence of bleeding can be suppressed by uniformizing the static surface tensions of the inks of the combination.
  • the dynamic surface tensions of the inks of the combination at a lifetime of 500 milliseconds preferably satisfy the above relationship in order that the inks can be made identical to each other in permeability into a recording medium with improved accuracy.
  • the ink set of the present invention described above is characterized in that the ink set has a plurality of inks each containing a dye, and has at least the first ink described above.
  • the concept of the ink set in the present invention includes an ink set in the state of ink cartridges each independently containing one ink of a plurality of inks and an ink set in the state of an ink cartridge integrally formed by combining a plurality of ink storing portions containing respectively a plurality of inks.
  • the ink cartridge may be formed integrally further with a recording head.
  • a state that ink cartridges each independently containing one ink of a plurality of inks are so formed as to be detachable from an ink jet recording apparatus is also included in the concept of the ink set of the present invention.
  • the ink set of the present invention has only to be formed so that at least the first ink and any other ink containing a dye can be used in combination, so the ink set is not limited to the above form, and may be in any form.
  • the ink set of the present invention may contain an ink containing a pigment in addition to the inks each containing a dye.
  • the ink containing a pigment is not used upon recording on a recording medium having an ink-receiving layer, so the ink may be free of any such dynamic surface tension characteristic as described above.
  • the first ink In the first embodiment of the present invention, the first ink must be adjusted so as to have any such dynamic surface tension characteristic as described above. In addition, in each of the second and third embodiments of the present invention, the first ink must be adjusted so as to have the dynamic surface tension characteristics (1) to (3) described above. Further, in the present invention, the ink A and the ink B determined from the a plurality of inks of which the ink set is composed as described above must be adjusted so as to have the dynamic surface tension characteristics described above. A constitution as in a conventional ink may be adopted except for the foregoing. Each of the components of which the ink of the present invention is composed will be described below.
  • Each of the inks of which the ink set of the present invention is composed preferably contains a surfactant as a penetrant.
  • the prepared ink requires to be adjusted so as to have the above-described change in dynamic surface tension.
  • the prepared ink requires to be adjusted so as to have the above-described change in dynamic surface tension.
  • alkyl trimethylammonium salt a dialkyl dimethylammonium chloride, and the like.
  • a fluorine-based compound a silicone-based compound, and the like.
  • the first ink In the first embodiment of the present invention, the first ink must be adjusted so as to have such dynamic surface tension characteristic as described above. In addition, in each of the second and third embodiments of the present invention, the first ink must be adjusted so as to have the dynamic surface tension characteristics (1) to (3) described above.
  • the first ink can achieve each of the dynamic surface tension characteristics described above by adjusting the dynamic surface tension of the ink with one or two or more types of surfactants listed above.
  • the dynamic surface tension of the first ink is adjusted particularly preferably with a polyoxyethylene alkyl ether or an ethylene oxide adduct of acetylene glycol among the above surfactants.
  • the polyoxyethylene alkyl ether is particularly preferably at least one selected from surfactants each represented by the following general formula (1) and surfactants each represented by the following general formula (2).
  • An ink containing such a surfactant is particularly suitable for achieving the compatibility between gradation and color uniformity when plain paper or the like is used as a recording medium because its dynamic surface tension changes to a large extent as a lifetime changes.
  • m, n, and a each independently represent an integer of 1 or more, and m + n represents an integer of from 14 to 20.
  • x, y, and b each independently represent an integer of 1 or more, and x + y represents an integer of from 15 to 21.
  • the HLB value of the above surfactant according to Griffin method is particularly preferably from 12.0 or more to 16.5 or less.
  • the hydrophilicity of the surfactant is so low that, for example, when the ink is contained, a state that the surfactant is dissolved in the ink cannot be maintained in some cases.
  • the hydrophilicity of the surfactant is so high that it is difficult to reduce the dynamic surface tension of the ink at a lifetime of 500 milliseconds.
  • the content (% by mass) of the surfactant in the first ink is preferably from 0.30% by mass or more to 2.0% by mass or less, or more preferably from 0.30% by mass or more to 1.5% by mass or less with respect to the total mass of the ink.
  • the content is less than 0.30% by mass, a member from which an ink flow path of an ink jet recording apparatus is formed is not sufficiently wet with the ink, and the discharge stability of the ink is lowered in some cases.
  • the lower limit of the content (% by mass) of the surfactant in the first ink is preferably 0.30% by mass or more, or more preferably 0.75% by mass or more with respect to the total mass of the ink.
  • the content is less than 0.30% by mass, the ink wettability of the plain paper cannot be sufficiently obtained, and color uniformity is reduced in some cases. Setting the content of the surfactant in the ink within the above range enables the ink to achieve the compatibility between excellent discharge stability and excellent image quality when plain paper or the like is used as a recording medium, in particular, excellent color uniformity.
  • the content (% by mass) of a surfactant in any ink except the first ink included in the ink set is formed is preferably from 0.10% by mass or more to 2.0% by mass or less, or more preferably from 0.30% by mass or more to 1.5% by mass or less, with respect to the total mass of the ink.
  • the preferable range of the content is, of course, not limited to the above range because the preferable range varies depending on the structure or HLB value of the surfactant.
  • the ink A and the ink B determined as described above must be adjusted so as to have the dynamic surface tension characteristics at a lifetime of 500 milliseconds described above.
  • the ink A and the ink B can achieve the dynamic surface tension characteristics described above by adjusting the dynamic surface tension of each of the inks with one or two or more types of surfactants listed above.
  • the content (% by mass) of a surfactant in each of the ink A and the ink B is preferably from 0.10% by mass or more to 2.0% by mass or less, or more preferably from 0.30% by mass or more to 1.5% by mass or less, with respect to the total mass of the ink from the viewpoint of ejection stability.
  • Each ink included in the ink set of the present invention preferably contains an aqueous medium as a mixed solvent of water and a water-soluble organic compound.
  • Deionized water ion-exchange water
  • the content (% by mass) of water in the ink is preferably from 30.0% by mass or more to 90.0% by mass or less with respect to the total mass of the ink in order that the ink can have suitable viscosity so as to be stably ejected, and clogging at the tip of a nozzle with the ink may be suppressed.
  • any water-soluble organic compound can be used as the water-soluble organic compound as long as the ink of the present invention is adjusted so as to have such dynamic surface tension characteristics as described above.
  • the content (% by mass) of the water-soluble organic solvent in the ink is preferably from 1.0% by mass or more to 50.0% by mass or less, and more preferably, from 3.0% by mass or more to 40.0% by mass or less, with respect to the total mass of the ink.
  • any one of the following can be used as the water-soluble organic compound.
  • Alcohols having 1 to 6 carbon atoms such as ethanol, isopropanol, 2-propanol, n-butanol, isobunanol, pentanol, and hexanol; carboxylic amides such as N,N-dimethylformamide and N,N-dimethylacetamide; ketones or ketoalcohols such as acetone, methylethylketone, and 2-methyl-2-hydroxypentane-4-one; cyclic ethers such as tetrahydrofuran and dioxane; alkylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2- or 1,3-propylene glycol, 1,2- or 1,4-butylene glycol, and polyethylene glycol; polyalcohols such as glycerin, 1,3-butanediol, 1,2- or 1,5-pentanediol, 1,2- or 1,6-hexan
  • a water-soluble organic compound having high permeability is particularly preferably used in order that the surface tension of the aqueous medium can be appropriately adjusted.
  • any one of the alcohols such as ethanol, 2-propanol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, and 1,6-hexanediol is particularly preferably used.
  • the first ink must be adjusted so as to have such dynamic surface tension characteristics as described above.
  • the first ink must be adjusted so as to have the dynamic surface tension characteristics (1) to (3) described above.
  • the first ink can be allowed to have such dynamic surface tension characteristics as described above also by adjusting the dynamic surface tension of the ink with one or two or more types of water-soluble organic compounds listed above.
  • the static surface tension of the aqueous medium in the first ink is preferably from 45 mN/m or more to 57 mN/m or less.
  • aqueous medium in ink refers to an aqueous medium excluding the coloring material and surfactant in the ink, that is, water and the water-soluble organic compound.
  • the static surface tension of the aqueous medium is higher than 57 mN/m, or is lower than 45 mN/m, in the case where plain paper having relatively large surface energy unevenness among various types of plain papers is used as a recording medium, gradation cannot be sufficiently obtained in some cases.
  • the static surface tension of the aqueous medium is higher than 57 mN/m, between a portion with high surface energy and a portion with low surface energy present near a portion where the ink is applied in the recording medium, the ink is apt to flow selectively into the portion with high surface energy. As a result, feathering is apt to occur, and the variation in area between dots becomes large, so gradation cannot be sufficiently obtained in some cases.
  • the static surface tension of the aqueous medium is lower than 45 mN/m, the surface tension of the aqueous medium in the ink is lower than that near the portion where the ink is applied in the recording medium, so the ink rapidly spreads, and, as a result, gradation is lowered in some cases.
  • the ink A and the ink B determined as described above from the a plurality of inks included in the ink set must be adjusted so as to have the dynamic surface tension characteristics at a lifetime of 500 milliseconds described above.
  • the ink A and the ink B can achieve the dynamic surface tension characteristics described above also by adjusting the dynamic surface tension of each of the inks with one or two or more types of water-soluble organic compounds listed above.
  • the coloring material to be used in each ink included in the ink set of the present invention is a dye.
  • the content (% by mass) of the dye in the ink is preferably from 0.1% by mass or more to 15.0% by mass or less, or more preferably from 1.0% by mass or more to 10.0% by mass or less, with respect to the total mass of the ink.
  • the dye is not particularly limited as long as the dye can be used as a coloring material for a general ink jet ink, and, for example, any one of a direct dye, an acid dye, a reactive dye, and a basic dye can be used. Examples of the dye usable in the present invention are indicated below for each color tone by the use of color index numbers. In addition, even dyes not described in any color index can be used as long as they are water-soluble.
  • C.I. Direct Yellow 8, 11, 12, 27, 28, 33, 39, 44, 50, 58, 85, 86, 87, 88, 89, 98, 100, 110, 132, 173, and the like.
  • C.I. Acid Yellow 1, 3, 7, 11, 17, 23, 25, 29, 36, 38, 40, 42, 44, 76, 98, 99, and the like.
  • C.I. Direct Red 2, 4, 9, 11, 20, 23, 24, 31, 39, 46, 62, 75, 79, 80, 83, 89, 95, 197, 201, 218, 220, 224, 225, 226, 227, 228, 229, 230, and the like.
  • C.I. Acid Red 6, 8, 9, 13, 14, 18, 26, 27, 32, 35, 42, 51, 52, 80, 83, 87, 89, 92, 106, 114, 115, 133, 134, 145, 158, 198, 249, 265, 289, and the like.
  • C.I. Food Red 87, 92, 94, and the like.
  • C.I. Direct Violet 107 and the like.
  • C.I. Direct Blue 1, 15, 22, 25, 41, 76, 77, 80, 86, 90, 98, 106, 108, 120, 158, 163, 168, 199, 226, 307, and the like.
  • C.I. Acid Blue 1, 7, 9, 15, 22, 23, 25, 29, 40, 43, 59, 62, 74, 78, 80, 90, 100, 102, 104, 112, 117, 127, 138, 158, 161, 203, 204, 221, 244, and the like.
  • C.I. Acid Orange 7, 8, 10, 12, 24, 33, 56, 67, 74, 88, 94, 116, 142, and the like.
  • C.I. Acid Red 111, 114, 266, 374, and the like.
  • C.I. Direct Orange 26, 29, 34, 39, 57, 102, 118, and the like.
  • C.I. Food Orange 3 and the like.
  • C.I. Reactive Orange 1, 4, 5, 7, 12, 13, 14, 15, 16, 20, 29, 30, 84, 107, and the like.
  • C.I. Disperse Orange 1, 3, 11, 13, 20, 25, 29, 30, 31, 32, 47, 55, 56, and the like.
  • C.I. Acid Green 1, 3, 5, 6, 9, 12, 15, 16, 19, 21, 25, 28, 81, 84, and the like.
  • C.I. Direct Green 26, 59, 67, and the like.
  • C.I. Food Green 3 and the like.
  • C.I. Reactive Green 5, 6, 12, 19, 21, and the like.
  • C.I. Disperse Green 6, 9, and the like.
  • C.I. Acid Blue 62, 80, 83, 90, 104, 112, 113, 142, 203, 204, 221, 244, and the like.
  • C.I. Reactive Blue 49 and the like.
  • C.I. Acid Violet 17, 19, 48, 49, 54, 129, and the like.
  • C.I. Direct Violet 9, 35, 47, 51, 66, 93, 95, 99, and the like.
  • C.I. Reactive Violet 1, 2, 4, 5, 6, 8, 9, 22, 34, 36, and the like.
  • C.I. Disperse Violet 1, 4, 8, 23, 26, 28, 31, 33, 35, 38, 48, 56, and the like.
  • C.I. Direct Black 17, 19, 22, 31, 32, 51, 62, 71, 74, 112, 113, 154, 168, 195, and the like.
  • C.I. Acid Black 2, 48, 51, 52, 110, 115, 156, and the like.
  • C.I. Food Black 1, 2, and the like.
  • Each ink included in the ink set of the present invention may contain an organic compound which is a solid at ordinary temperature, such as trimethylolethane or trimethylolpropane, or a nitrogen-containing compound such as urea or ethylene urea in addition to such components as described above as required.
  • the ink of the present invention may contain any one of the various additives such as a pH adjustor, a rust inhibitor, an antiseptic, a mildewproofing agent, an antioxidant, an antireducing agent, an evaporation accelerator, and a chelating agent in addition to such components as described above in order that the ink may have desired physical property values.
  • the ink of the present invention is particularly suitably used for an ink jet recording method in which recording is performed on a recording medium by ejecting the ink by an ink jet recording system.
  • Examples of the ink jet recording method include a method involving applying mechanical energy to ink to eject the ink and a method involving applying thermal energy to ink to eject the ink.
  • the ink of the present invention can exhibit outstanding meritorious effects when being used in the ink jet recording method involving the use of thermal energy.
  • An ink cartridge of the present invention is characterized by including an ink storing portion for storing the ink of the present invention.
  • a recording unit of the present invention is characterized by including: an ink storing portion for storing the ink of the present invention; and a recording head for ejecting the ink.
  • a significant effect can be obtained particularly when the recording unit is such that the recording head ejects the ink by applying thermal energy to the ink.
  • An ink jet recording apparatus of the present invention is characterized by including: an ink storing portion for storing the ink of the present invention; and a recording head for ejecting the ink.
  • a significant effect can be obtained particularly when the ink jet recording apparatus is such that the recording head ejects the ink by applying thermal energy to the ink.
  • An ink jet recording apparatus is constituted of a sheet feeding portion, a conveying portion, a carriage portion, a sheet delivery portion, a cleaning portion, and an external packaging portion for protecting them and providing the apparatus with a design to achieve a role of each mechanism.
  • an external packaging portion for protecting them and providing the apparatus with a design to achieve a role of each mechanism.
  • FIG. 2 is a perspective view of an ink jet recording apparatus.
  • FIGS. 3 and 4 are views for illustrating the internal mechanism of an ink jet recording apparatus.
  • FIG. 3 is a perspective view seen from an upper right portion, and
  • FIG. 4 is a side sectional view of the ink jet recording apparatus.
  • a sheet When a sheet is to be fed in the recording apparatus, only the predetermined number of recording media is sent to a nip portion composed of a sheet feeding roller M2080 and a separating roller M2041 in the sheet feeding portion including a sheet feeding tray M2060 (see FIGS. 2 and 4 ).
  • the sent recording media are separated at the nip portion, and only the uppermost recording medium is conveyed.
  • the recording medium sent to the sheet conveying portion is guided by a pinch roller holder M3000 and a paper guide flapper M3030 to be sent to a roller pair composed of a conveying roller M3060 and a pinch roller M3070.
  • the roller pair composed of the conveying roller M3060 and the pinch roller M3070 are rotated by an LF motor E0002, and the rotation causes the recording medium to be conveyed on a platen M3040 (see FIGS. 3 and 4 ).
  • a carriage portion Upon formation of an image, a carriage portion places a recording head H1001 (see FIG. 5 ) at a position where a target image is formed, and ink is ejected onto a recording medium in accordance with a signal from an electric substrate E0014 (see FIG. 3 ).
  • the detailed constitution of the recording head H1001 will be described later. While recording is performed with the recording head H1001, an image is formed on the recording medium by alternately repeating primary scanning in which a carriage M4000 (see FIG. 3 ) scans the recording medium in a column direction and secondary scanning in which the transport roller M3060 (see FIGS. 3 and 4 ) transports the recording medium in a row direction.
  • the recording medium is fastened at a nip between a first delivery roller M3110 and a spur M3120 in a delivery portion (see FIG. 4 ), and is transported so as to be discharged to a delivery tray M3160 (see FIG. 2 ).
  • a cleaning portion cleans the recording head H1001.
  • the cleaning portion sucks the ink or the like from the recording head H1001 by activating a pump M5000 (see FIG. 3 ) in a state that a cap M5010 (see FIG. 3 ) is brought into close contact with a ejection orifice of the recording head H1001.
  • a pump M5000 see FIG. 3
  • the cleaning portion sucks the ink remaining in the cap M5010 in a state that the cap M5010 is opened, the fixing of the ink or any other detrimental effects are prevented from occurring.
  • the constitution of a head cartridge H1000 will be described (see FIG. 5 ).
  • the head cartridge H1000 includes the recording head H1001, a means for mounting ink cartridge H1900, and a means for supplying ink from the ink cartridge H1900 to the recording head.
  • the head cartridge H1000 is detachably mounted on the carriage M4000 (see FIG. 3 ).
  • FIG. 5 shows how the ink cartridges H1900 are mounted on the head cartridge H1000.
  • the ink jet recording apparatus forms an image by means of, for example, each of yellow, magenta, cyan, black, light magenta, light cyan, and green inks, so the ink cartridges H1900 is independently prepared for each of the seven colors.
  • each ink cartridge H1900 is detachable from the head cartridge H1000.
  • the ink cartridge H1900 can be detached in a state that the head cartridge H1000 is mounted on the carriage M4000 (see FIG. 3 ).
  • FIG. 6 shows an exploded perspective view of the head cartridge H1000.
  • the head cartridge H1000 is constituted of a recording element substrate, a plate, an electric wiring substrate H1300, a cartridge holder H1500, a flow path forming member H1600, a filter H1700, and a seal rubber H1800.
  • the recording element substrate is composed of a first recording element substrate H1100 and a second recording element substrate H1101, and the plate is composed of a first plate H1200 and a second plate H1400.
  • Each of the first recording element substrate H1100 and the second recording element substrate H1101 is an Si substrate having a plurality of recording elements (nozzles) for ejecting ink which are formed on one side thereof by means of photolithography.
  • Electric wiring formed of Al or the like for supplying power to each recording element is formed by means of a film formation technology or the like, and a plurality of ink flow paths corresponding respectively to the recording elements are also formed by means of photolithography. Further, ink supply orifices for supplying ink to the plurality of ink flow paths are formed so as to open on the rear surface.
  • FIG. 7 is an enlarged front view for illustrating the constitution of each of the first recording element substrate H1100 and the second recording element substrate H1101.
  • Reference characters H2000 to H2600 denote recording element trains (hereinafter referred to also as nozzle trains) each supplying a different ink color.
  • the first recording element substrate H1100 has nozzle trains for three colors: the nozzle train H2000 for yellow ink; the nozzle train H2100 for magenta ink; and the nozzle train H2200 for cyan ink.
  • the second recording element substrate H1101 has nozzle trains for four colors: the nozzle train H2300 for light cyan ink; the nozzle train H2400 for black ink; the nozzle train H2500 for green ink; and the nozzle train H2600 for light magenta ink.
  • Each nozzle train includes 768 nozzles arranged at intervals of 1,200 dpi (dot/inch; reference value) in the direction in which a recording medium is conveyed, and each nozzle ejects about 2 pl of ink.
  • An opening area in each ejection orifice is set to be about 100 ⁇ m 2 .
  • the first recording element substrate H1100 and the second recording element substrate H1101 are bonded and fixed to the first plate H1200, and ink supply orifices H1201 for supplying ink to the first recording element substrate H1100 and the second recording element substrate H1101 are formed on the first plate H1200.
  • the second plate H1400 having openings is also bonded and fixed to the first plate H1200.
  • the second plate H1400 holds the electric wiring substrate H1300 in such a manner that the electric wiring substrate H1300, the first recording element substrate H1100, and the second recording element substrate H1101 are electrically connected.
  • the electric wiring substrate H1300 applies an electrical signal for causing each of the nozzles formed on the first recording element substrate H1100 and the second recording element substrate H1101 to eject ink.
  • the electric wiring substrate H1300 has: electric wiring corresponding to each of the first recording element substrate H1100 and the second recording element substrate H1101; and an external signal input terminal H1301 which is positioned at an end portion of the electric wiring to receive an electrical signal from the ink jet recording apparatus.
  • the external signal input terminal H1301 is positioned and fixed to the back surface side of the cartridge holder H1500.
  • the flow path forming member H1600 is fixed by means of, for example, ultrasonic welding to the cartridge holder H1500 for holding the ink cartridge H1900.
  • an ink flow path H1501 passing from the ink cartridge H1900 to the first plate H1200 is formed.
  • the filter H1700 is provided at an end portion on the ink cartridge side of the ink flow path H1501 engaged with the ink cartridge H1900, so the filter H1700 prevents dust from entering from the outside.
  • the seal rubber H1800 is mounted on the portion at which the ink flow path H1501 is engaged with the ink cartridge H1900 to prevent ink from evaporating from the portion.
  • the head cartridge H1000 is formed by, for example, causing a cartridge holder portion and the recording head H1001 to adhere to each other.
  • the cartridge holder portion is composed of the cartridge holder H1500, the flow path forming member H1600, the filter H1700, and the sealing rubber H1800.
  • the recording head H1001 is composed of the first recording element substrate H1100 and the second recording element substrate H1101, the first plate H1200, the electric wiring substrate H1300, and the second plate H1400.
  • the thermal ink jet system is particularly applicable to the on-demand type.
  • at least one driving signal which corresponds to recording information and triggers a rapid temperature rise exceeding nucleate boiling is applied to electrothermal transducers arranged corresponding to liquid paths holding ink, to thereby cause the electrothermal transducer to generate thermal energy.
  • the ink is caused to generate film boiling.
  • an air bubble in the ink can be formed so as to be in one-to-one correspondence with the driving signal.
  • the growth and contraction of the air bubble cause the ink to be ejected through an opening for ejection, thereby forming at least one droplet.
  • the driving signal is more preferably of a pulse shape because the growth and contraction of an air bubble can be performed immediately and appropriately, and hence ink can be discharged with excellent responsiveness.
  • the ink of the present invention can be preferably used not only in a recording head according to the thermal ink jet system but also in such an ink jet recording apparatus utilizing mechanical energy as described below.
  • the ink jet recording apparatus in such a form includes: a nozzle-forming substrate having a plurality of nozzles; a pressure-generating element placed opposite to the nozzles and composed of a piezoelectric material and a conductive material; and ink with which the periphery of the pressure-generating element is filled.
  • the pressure-generating element is displaced by an applied voltage to eject the ink from the nozzles.
  • the ink jet recording apparatus is not limited to such apparatuses as described above in which a recording head and an ink cartridge are separated, and may be one in which a head and an ink cartridge are so integrated as to be inseparable. Further, the ink cartridge may be separably or inseparably unified with the recording head to be mounted on a carriage, or may be mounted on a fixing portion of an ink jet recording apparatus to supply ink to a recording head through an ink supply member such as a tube.
  • the ink cartridge When the ink cartridge is provided with a constitution for applying a preferable negative pressure to the recording head, it may be configured as follows.
  • an absorber may be placed in an ink storing portion of the ink cartridge, or the ink cartridge may have a flexible ink storage bag and a spring portion for exerting biasing power in the direction of expanding the internal volume of the bag.
  • the ink jet recording apparatus may adopt a serial recording system, or may be in the form of a line printer in which recording elements are aligned over the range corresponding to the entire width of a recording medium.
  • HLB 20 ⁇ formula weight of hydrophilic group of surfactant / molecular weight of surfactant
  • Table 1 collectively shows the structure of the main component of each surfactant, and, when the structure of the surfactant corresponded to the general formula (1) or the general formula (2), values of m, n, a, and m + n, or values of x, y, b, and x + y.
  • EMALEX 1615 is a surfactant manufactured by NIHON EMULSION Co., Ltd.
  • Acetylenol E100 is a surfactant manufactured by Kawaken Fine Chemicals Co., Ltd.
  • EMULMIN CO-50 and EMULMIN NL90 are each a surfactant manufactured by Sanyo Chemical Industries Ltd.
  • NIKKOL BT-7 is a surfactant manufactured by Nikko Chemicals co., ltd.
  • Polyoxyethylene oleyl ether - - - - - - - - - EMULMIN NL90 1.0
  • EMULMIN CO-50 and EMULMIN NL90 are each a surfactant manufactured by Sanyo Chemical Industries Ltd.
  • NIKKOL BT-7 is a surfactant manufactured by Nikko Chemicals co., ltd. Table 2 (Unit: %) Cyan ink C1 C2 C3 C4 C5 C.I.
  • the (1) dynamic surface tension of each of the inks obtained above at a lifetime of 50 milliseconds, and the (2) dynamic surface tension of each of the inks at a lifetime of 500 milliseconds were measured.
  • the difference ⁇ ⁇ [(1) - (2)] between the dynamic surface tensions (1) and (2) was determined.
  • An apparatus for measuring a dynamic surface tension by a maximum bubble pressure method (Bubble Pressure Tensiometer BP2; manufactured by KRUSS) was used in the measurement.
  • the dynamic surface tensions were each measured at 25°C. Table 5 shows the results of the evaluation for dynamic surface tensions.
  • An ink cartridge was filled with each of the inks obtained above, and was mounted on a modified apparatus of an ink jet recording apparatus iP3100 (manufactured by Canon Inc.) in which ink is ejected from a recording head by the action of thermal energy. After that, recording was performed on a recording medium (PR-101; manufactured by Canon Inc.) so that the amount of applied ink per one pixel at a resolution of 600 ppi was 10 ng.
  • the lightness of the resultant image was measured with a Spectrolino (manufactured by Gretag Macbeth) by using a D65 as a light source at a field of view of 2°. Table 5 shows the results of the measurement of the lightness.
  • an ink corresponding to the first ink in the present invention is each of the inks C1 to C5, M2, and Y1.
  • the image formed by using each of the inks corresponding to the first ink in the present invention at a recording duty of 100% on a plain paper had good color uniformity.
  • the recording apparatus and recording medium used in the above image formation was an ink jet recording apparatus iP3100 and PPC paper Office Planner (each manufactured by Canon Inc.).
  • Ink sets were obtained by using in combination two types of inks selected from the inks C1 to C5, M1 to M8, and Y1 to Y3 obtained above as shown in Table 6 below. Then, as shown in Table 6, between two types of inks included in the ink set, an ink having relatively higher lightness was defined as an ink A, and an ink having relatively lower lightness was defined as an ink B.
  • Table 6 showed the value of lightness of each of the ink A and the ink B, the dynamic surface tension ⁇ a of the ink A at a lifetime of 500 milliseconds, the dynamic surface tension ⁇ b of the ink B at a lifetime of 500 milliseconds, and the difference ( ⁇ a - ⁇ b ) between the dynamic surface tensions.
  • An ink cartridge was filled with each of the ink A and the ink B of the a plurality of inks included in the ink set, and was mounted on a modified apparatus of an ink jet recording apparatus iP3100 (manufactured by Canon Inc.) in which ink was ejected from a recording head by the action of thermal energy. After that, an image shown in FIG. 1 was formed on a recording medium (PR-101; manufactured by Canon Inc.) in four paths. The resulting recorded matter was visually observed and evaluated for bleeding. Criteria for the evaluation for bleeding are as described below. Table 6 shows the results of the evaluation.
  • the ink M8 has a dynamic surface tension of 41 mN/m at 500 milliseconds while each of the inks C1 and Y1 has a dynamic surface tension of 37 mN/m at 500 milliseconds.
  • an image was at an unpreferable level because bleeding was observed over the entirety of the image.
  • an image was at an acceptable level, though bleeding was slightly observed on part of the image.
  • the absolute values of the differences in dynamic surface tension at 500 milliseconds between the inks were 4 for both of them, but the extents to which bleeding occurred owing to a lightness relationship between the inks were different from each other.
  • An ink set was obtained by using in combination three types of inks selected from the inks C1, C2, M1, M2, M4, and Y1 to Y3 obtained above as shown in Table 7 below. Then, as shown in Table 7, for each of all (three) combinations of two types of inks selected from the three types of inks included in the ink set, an ink having relatively higher lightness was defined as an ink A, and an ink having relatively lower lightness was defined as an ink B.
  • An ink cartridge was filled with each of the ink A and the ink B of the a plurality of inks included in the ink set, and was mounted on a modified apparatus of an ink jet recording apparatus iP3100 (manufactured by Canon Inc.) in which ink was ejected from a recording head by the action of thermal energy. After that, an image shown in FIG. 1 was formed on a recording medium (PR-101; manufactured by Canon Inc.) in four paths. A recorded matter obtained by using each of all (three) combinations of two types of inks selected from the three types of the inks included in the ink set, was visually observed and evaluated for bleeding. Criteria for the evaluation for bleeding are as described below. Table 7 shows the results of the evaluation.
  • Example 25 including a combination of two types of inks among the three types of inks included in an ink set where the value of ⁇ a - ⁇ b was -4, the following bleeding performance was exhibited. That is, in a combination of two types of inks where the value of ⁇ a - ⁇ b was -4, an image was at an acceptable level while bleeding was slightly observed on part of the image; and, in the other combinations of two types of inks, no bleeding was observed over the entirety of an image. Accordingly, in Example 25, bleeding was comprehensively at an acceptable level.
  • Reference Example 1 including a combination of two types of inks among three types of inks included in an ink set where the value of ⁇ a - ⁇ b was 6, bleeding was observed over the entirety of an image in that combination, and the bleeding was comprehensively at an unacceptable level.
  • the ink set includes a plurality of aqueous inks each containing a dye, and has at least a first aqueous ink containing a dye, wherein the difference between the dynamic surface tension of the first aqueous ink at a lifetime of 50 milliseconds and the dynamic surface tension of the first aqueous ink at a lifetime of 500 milliseconds is 7 mN/m or more; and, between the first aqueous ink and at least one type of aqueous ink except the first aqueous ink included in the ink set, dynamic surface tension ⁇ a (mN/m) of an ink A having relatively higher lightness at a lifetime of 500 milliseconds and dynamic surface tension ⁇ b (mN/m) of an ink B having relatively lower lightness at a lifetime of 500 milliseconds satisfy -5 ⁇ ( ⁇ a - ⁇ b ) ⁇ 3.

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Claims (13)

  1. Tintensatz umfassend eine Mehrzahl wässriger Tinten, wobei jede Tinte einen Farbstoff als ein färbendes Material umfasst, wobei:
    der Tintensatz wenigstens eine erste wässrige Tinte aufweist, die einen Farbstoff als ein färbendes Material umfasst;
    ein Unterschied zwischen der dynamischen Oberflächenspannung der ersten wässrigen Tinte bei einer Lebenszeit von 50 Millisekunden und der dynamischen Oberflächenspannung der ersten wässrigen Tinte bei einer Lebenszeit von 500 Millisekunden 7 mN/m oder mehr ist; und
    zwischen der ersten wässrigen Tinte und wenigstens einem Typ der in dem Tintensatz beinhalteten wässrigen Tinte ausgenommen der ersten wässrigen Tinte, die dynamische Oberflächenspannung Ya (mN/m) einer Tinte A mit einer relativ höheren Helligkeit bei einer Lebenszeit von 500 Millisekunden und der dynamischen Oberflächenspannung Yb (mN/m) einer Tinte B mit einer relativ geringeren Helligkeit bei einer Lebenszeit von 500 Millisekunden eine Beziehung von -5 ≤ (Ya - Yb) ≤ 3 erfüllen.
  2. Tintensatz nach Anspruch 1, wobei:
    die erste wässrige Tinte zusätzlich die folgenden Bedingungen (1) und (2) erfüllt:
    (1) die dynamische Oberflächenspannung bei einer Lebenszeit von 50 Millisekunden ist von 42 mN/m oder mehr bis weniger als 49 mN/m, und
    (2) die dynamische Oberflächenspannung bei einer Lebenszeit von 500 Millisekunden ist von 28 mN/m oder mehr bis 38 mN/m oder weniger.
  3. Tintensatz nach Anspruch 2, wobei der Tintensatz wenigstens drei Typen wässriger Tinten umfasst, wobei jede Tinte einen Farbstoff als ein färbendes Material umfasst; und
    von zwei Typen der wässrigen Tinte, die willkürlich aus den wenigstens drei Typen der in dem Tintensatz beinhalteten wässrigen Tinten ausgewählt werden, die dynamische Oberflächenspannung Ya (mN/m) einer Tinte A mit einer relativ höheren Helligkeit bei einer Lebenszeit von 500 Millisekunden und der dynamischen Oberflächenspannung Yb (mN/m) einer Tinte B mit einer relativ geringeren Helligkeit bei einer Lebenszeit von 500 Millisekunden eine Beziehung von -5 ≤ (Ya - Yb) ≤ 3 erfüllen.
  4. Tintensatz nach einem der Ansprüche 1 bis 3, wobei jede der Tinten einen nichtionischen oberflächenaktiven Stoff enthält.
  5. Tintensatz nach Anspruch 4, wobei der nichtionische oberflächenaktive Stoff wenigstens einer ausgewählt aus der Gruppe bestehend aus den oberflächenaktiven Stoffen dargestellt durch die folgenden allgemeinen Formeln (1) und (2) ist:
    Figure imgb0009
     (in der allgemeinen Formel (1) stellen m, n und a jeweils unabhängig eine ganze Zahl von 1 oder mehr dar, und m + n stellt eine ganze Zahl von 14 bis 20 dar).
    Figure imgb0010
     (in der allgemeinen Formel (2) stellen x, y und b jeweils unabhängig eine ganze Zahl von 1 oder mehr dar, und x + y stellt eine ganze Zahl von 15 bis 21 dar).
  6. Tintensatz nach Anspruch 4 oder 5, wobei der HLB-Wert jeder der nichtionischen oberflächenaktiven Stoffe gemäß dem Griffin-Verfahren 12,0 oder mehr und 16,5 oder weniger ist.
  7. Tintensatz nach einem der Ansprüche 4 bis 6, wobei der Gehalt des oberflächenaktiven Stoffs in der ersten wässrigen Tinte basierend auf der gesamten Masse der Tinte 0,30 Massen-% oder mehr und 2,0 Massen-% oder weniger ist, der Gehalt des oberflächenaktiven Stoffs in der Tinte A basierend auf der gesamten Masse der Tinte 0,10 Massen-% oder mehr und 2,0 Massen-% oder weniger ist, und der Gehalt des oberflächenaktiven Stoffs in der Tinte B basierend auf der gesamten Masse der Tinte 0,10 Massen-% oder mehr und 2,0 Massen-% oder weniger ist.
  8. Tintenstrahlaufzeichnungsverfahren umfassend das Ausstoßen von Tinte durch ein Tintenstrahlverfahren, wobei die Tinte wässrige Tinten umfasst, aus welchen der Tintensatz gemäß einem der Ansprüche 1 bis 7 zusammengesetzt ist.
  9. Tintenstrahlaufzeichnungsverfahren nach Anspruch 8, wobei das Tintenstrahlverfahren ein Tintenstrahlaufzeichnungsverfahren ist, in welchem die Tinte aus einem Aufzeichnungskopf durch die Wirkung thermischer Energie ausgestoßen wird.
  10. Tintenkartusche umfassend einen Tintenspeicherabschnitt für die Speicherung von Tinte, wobei die Tinte, die in dem Tintenspeicherabschnitt enthalten ist, eine der wässrigen Tinten ist, welche den Tintensatz gemäß einem der Ansprüche 1 bis 7 aufbaut.
  11. Aufzeichnungseinheit umfassend:
    einen Tintenspeicherabschnitt für die Speicherung von Tinte; und
    einen Aufzeichnungskopf für den Ausstoß der Tinte,
    wobei die Tinte, die in dem Tintenspeicherungsabschnitt enthalten ist, die wässrigen Tinten umfasst, aus welchen der Tintensatz gemäß einem der Ansprüche 1 bis 7 aufgebaut ist.
  12. Tintenstrahlaufzeichnungsgerät umfassend:
    einen Tintenspeicherabschnitt für die Speicherung von Tinte; und
    einen Aufzeichnungskopf für den Ausstoß der Tinte,
    wobei die Tinte, die in dem Tintenspeicherabschnitt enthalten ist, die wässrigen Tinten umfasst, aus welchen der Tintensatz gemäß einem der Ansprüche 1 bis 7 aufgebaut ist.
  13. Verwendung einer ersten wässrigen Tinte mit einem Farbstoff in einem Tintensatz, der eine Mehrzahl von wässrigen Tinten aufweist, die jeweils einen Farbstoff umfassen, wobei:
    ein Unterschied zwischen der dynamischen Oberflächenspannung der ersten wässrigen Tinte bei einer Lebenszeit von 50 Millisekunden und der dynamischen Oberflächenspannung der ersten wässrigen Tinte bei einer Lebenszeit von 500 Millisekunden 7 mN/m oder mehr ist; und
    zwischen der ersten wässrigen Tinte und wenigstens einem Typ der in dem Tintensatz beinhalteten wässrigen Tinte ausgenommen der ersten wässrigen Tinte, die dynamische Oberflächenspannung Ya (mN/m) einer Tinte A mit einer relativ höheren Helligkeit bei einer Lebenszeit von 500 Millisekunden und der dynamischen Oberflächenspannung Yb (mN/m) einer Tinte B mit einer relativ geringeren Helligkeit bei einer Lebenszeit von 500 Millisekunden eine Beziehung von -5 ≤ (Ya - Yb) ≤ 3 erfüllen.
EP08155981.7A 2007-05-11 2008-05-09 Tintensatz, Tintenstrahlaufzeichnungsverfahren, Tintenpatrone, Aufzeichnungseinheit, Tintenstrahlaufzeichnungsverfahren und wässrige Tinte Not-in-force EP1990382B1 (de)

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